Manufacture of chlorinated products of xylene, aldehydobenzoic acids, and dyestuffs therefrom.



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To "all whornit may Be it .lmownthat we, JULrus Sonmnnm,

.firofessor of chemistry, a citizen of the'Swiss epublic, residing at Borngasse .7, Bergen, near Frankiort-on-the-Main, Germany, and MAX Fi scnnn, Ph. D., a citizen of the Swiss Republic, 'resi at present at Roederbergweg 139, Frank ort-on-the-Main, Germany, have invented certain newand useful Improvements in" the Manufacture of Chlorinated Products of-Xylene, Aldehydobenzoic Acids, and Dyestufi's Therefrom, of which the followin is a full description. 7

We have covered that xylenes halogenated in the nucleus, such as mono-, di-, tri- .-and tetrachloroxylenesmay at elevated temperatures and. medium exposure to light be urther chlorinated to new chlorin derive, .tives with four chlorin atoms in the side 'direct orafter saponificationto the correqsgfnding dialdehydes R(CHO) previously c orinated in the nucleus, arendensed with o-oxycarbonic acids such as resotinic' acid, and subsequently oxidized with sodium nitrite in concentrated sulfuric acid solution; blue dye-stufis are obtained which may.

I be afterchrolned.

e above mentioned chlorination in the side chains may also be, carried on until five ehlorin atomshave been introduced in the side chains; these new chlorin'derivatives I 1 4 \cclej may subsequently-,- that isfeither direct or after saponification, be condensed with o-oxgcarhonic acids j to the corresponding- -46 ydobenzoie acids 0110 I "s n-1,, V, chlorinated in'the nucleus, andmay be oxidized with sodium nitrite tonew' {bright bluish-violet dyestufis. p

Instead f start'ng from the ready xylenes i ichloi'inated in the-nucleus, it is also feasible einanate from the o-,-mor p-xylene, or

inylene as the-principal ingredient and n the dark'up toft e"des ired-nufdber of ogen atoms in the nucleus,"and then to I lpeo lfl catlon ot hotter: Patent. f' m1n m Kay 18, me. new It. emeoi fronrtechnical xylene, (which latter conta ns and I%et;e nted Mal-.13, 1917.

carry through the-g chains pt elevatedex osure to lighjt' he rocesso -,-,-*,\vc rking is illustrated by the fol owing les;

i lorinating in the side :mpefatures and under Production" of is rmzmzmmm z m"- chlmu benzene.

Example I; Unde1 the influence of light a current of chloringii led into trichloro-mxylene or its analogous product prepared with technical xylene .at 120 C. until the increase in weight or in density announces the introduction of four chlorin atoms. The

- colorless liquor possessing a boilin oint of 330331 C. may be purifiedb? dls'tlllation.

r In the same mannarthe fol owing bodies derived from pure' or. mixed omand 'p-xylenes or from th 5 mixtures contained in ,20 chains; If these bodies B(CHC1,),', either th -t d 'iml l m obtained;

(l, meltin'g 1,2 di (dichlorome thyl) o'robenzenel,

boiling oint 22421 0., i

a of chlorin is 1ed into trichloro-mxylene or into the. analogous product derived 'eglrxy'lene until the in crease inweigh i1 density announces the introduction 'of five-c liloi'inatqms. ,The distilled product resents-a colorlessliquor W'itha boiling p'omt of 8 9 40? (3.;

' Example III Un ier theiniluence of fight ambit 1151mm themed-em of-light and ate temperatum of Qfacurrent of chlorin' is led into idi chloro-m-xylene or into the IProduct derived from technical xylene lint the in weight'or in density ash and stirring for 8 hours.

- Production, 0 f

7 Exam is P rts of triciuomlde f.

l1'yd'1 -m-enzoic acid are allow announces the introduction of five ehlorin atoms. The distilled product a boiling oint of 321-322" C.

The ollowing analogous products have been obtained in the same manner:

1 dichlorometh yl 4 trichloromethyl-di chlorobenzene, bolling point 322-324 C. 1 dichloromethyl 4 trichloromethyl-trichlorobenzene, decomposes at 360 0.,

,melting point 120 C ese described chlorinated products atoms in the accordin to starting rom 1 th containing only three chlorin nucleus may also be obtained a new manner of working by xylene. I

Production of 1-dahzmmm z-amcuerometkybtfichloroberwene.

Example IV: m-xylene or the technical to a current of chlorin in total darkness and cooled down to 045 three halogen atoms wh ch cannot be substituted 'by means of potassium methylate. is raised to 120 C. and under: the influence of light the chlorinating is continued until further five chlorin atoms have been introduced which may be substituted by means of. potassium methylate;

aon'version 'ofz-diahzm m aatrieuom 'methyl-trichtorobeneene into tn delaydo-m-benzoc'c 1 Example V: Thechlorinated product is dissolve parts of concentrated ohloro-ald in about 10 sulfuric acid while heating to 90100 (.1.

The aldehydobenzoic acid is precipitated by ice water and recrystallized out of hot water in form of .small shining leaflets. It melts at 214 C. and dissolvesreadily in alkali and in carbonate of soda.

1 ed to act on 30 parts of o-cresotinicacid and -50 parts of concentrated sulfuric acid until the aldeyde has disappeared. The leuco compound 1n caustic 100-130 0; and vuntil further five w -Fl theemapating 'dobenzoic acids chlorinated in the nucleus,

is oxidized b 7 parts of sodium nitrite, finally heating until the formation of the dyestufl" is complete. The dyestufl is dpredissolves soda with a bluish-violet color. Out of acid baths it dyes wool brownishred shades which turn an intense bluishviolet by treating with bichrolnate.

In the place of trichloroaldehydo-menzoic acid it isjfeasihle to use 'l-dichlorohyl 3 trichloromethyltrichlorobenzene and hereafter cooling down with o-cresotinic acid. As oxidizlng agents nitric acid, nitrated compounds or concentrated or fuming sulfuric acidfmay likewise be employed.

' en starting from dichloroaldehydo-mbenzoic acid or from 1-dichloromethyl-3- trichloromethyldichlorobenzene, otherwise wor g according to the same method, an

formed, we declare that what we claim is he process .ofproducing dyestuffs of the triphenylmethane series which consists in chlorinating xylenes chlorinated in the nucleus, at elevated temperatures (100430 and'under exposure to light until further four chlorin atoms have been introduced in the side chains, then subsequently condensing these new chlorin derivatives with ortho-cresotinic acid to the leuco compound after saponification to chlorinated dialdehydes by means of concentrated sulfuric acid, and

pound with sodium nitrite inconcentrated,

sulfuric acid solution dyestuif, substantial I "2. The process of stufls of the triphen consists in the nucleus :at

to the above describedas described. producing newd ee evated temperatures under exposure to light 4 chlorin atoms have been Introduced in the condensing these new chlorin-de-v oxidizing thfe leuco com;

ylmethane WhlChf I in chlorinatm xylenes chlorinated s1de" chains, then subse brownish-orange color and bonic acids by means of concentrated sul 1 mm nitrite ric acid .to t, l iealeuco-cog goundgand ally oxidizing same with I concentrated sulfuric acid'solution to the above described dyestufi, substantially as oducts for manufacturing erein described new aldehywhich are solnble in hot'water, being ob tained therefrom infine crystals, dissolving also in cold diluted alkalis and alkaline ca'rbonates, substantially as described.

4. As new emanating products for manufacturing the new triphenylmethane dyestuffs herein described, produced from aldehydobenzoic acids chlorinated in the nucleus and" ortho-cresotinicacid, being orange-red powders in the dry state, dise solving in vwater with a yellow-brown color,

in diluted alkali with an intense violet-blue color, dyeing wool from an acid bath a brown-red shade, and yieldin after chroming bright, beautify l, violet-b ue dyein of very good iastnessuo'washing and mifiing, substantially as des :ribed.

In witness whereof we have hereunto signed our names this 10th day of April,

1916, in the presence of tworsubscribing wit- 3 0 I nesses. k

JULIUS SCHMIDLIN.

MAX FISCHER.

w Witnesses:

V JEAN GR N CARL GRUND. 

